Nitrogen containing resinous products from keto-amides



United States Patent OfiFice 2,757,164 Patented July 31, 1 956 NITROGEN CONTAINING RESIN OUS PRODUCTS FROM KETO-AMIDES H rman B oc Ch o, and Ra p B- T omp on,

Hinsdale, Ill., assignors to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application September 27, 1954,

. Serial No. 458,664

ill Claims. .(Cl. .260 .-65)

duction of resinous materials useful in many arts such as components of coating compositions, as raw materials in the formation of moldable plastic-like objects, as plas ticizers in rubber compositions and for other uses common to resins of the present type. More particularly, the invention concerns a new class of resinous product characterized either 'as a thermosetting or as thermoplastic type depending upon the structure of the reactants ashereinafter set forth, said resin being formed by the inter-condensation of keto-arnides or by condensing a ketoarnide with an aromatic polyketone and/or a polysulfonamide at reaction conditions resulting in the liberation of water as a by-product of the reaction and the condensation of the reactants to form said resinous product.

The formation of the present resinous condensation product is ordinarily efiiected inthe absence of any recognized catalytic agent. One object of this invention, therefore, is to prepare a thermosetting or thermoplastic resinous material (depending upon the conditions of reaction and the structure and type of ketoand sulfonamide reactants employed) 'by means of a simple condensation reaction in the absence of any added catalytic agent,-

thereby eliminating the necessity of removing or recovering catalyticmaterial from the finished resinous'product '-following the condensation reaction in which the resin is formed.

his another object ofthe invention to provide'a process for the production of resinous materials useful inthe preparation of coating compositions such as paints and "varnishes, as plasticizers for synthetic'or natural rubber,

as raw materials in the formation of molda-bleplasticlike objects, as adhesives and for other uses of like character.

In one of its specific applications, the present invention concerns aprocess for the preparation of a resinous material which comprises reacting anon-intracondensable keto-amide with at least onecornpound selected from the group consisting of: (1) a member of the class consisting of -sa-id aforementioned keto-arnides, *(2) an aromatic polyketone and (3) -a polysulfonamide in which the amide groups contain at least one replaceablehydrogen atom attached to the nitrogen atom of the said groups at condensation reaction conditions resulting in the formation of said resinous material.

Amore 'specific embodiment of the invention relates to 'a process which comprises reacting an aromatic diketone with a disulfonamide and a ketosulfonamidelin which the keto carbonyland sulfonamide groups are separatedby at least 4 carbon atoms in the aliphatic chain, and whereineach sulfonamide groups contains at least one replaceable hydrogen atom attached to the nitrogen atom of said group at a temperature of from-about 50 to about of the hydrogen atoms of 350 C., forming as a result of the reaction a thermoplastic resinous condensation product.

Other embodiments of .the invention relating to specific reactants and to certain means of effectipg the condensation reaction will be hereinafter referred to in the following further description of the invention.

In accordance with the present process, an aromatic polyketone, wherein the keto groups are attached either to .an aryl nucleus or to a carbon-atom in the side chain attached to the aryl nucleus, together with a polysulfonamide of eitheraliphatic, aromatic, alicyclic or heterocyclic structure and containing at least one condensable or replaceable hydrogen atom per amide group are reacted at condensation reaction conditions with a ';k;etoamideo'f the class hereinafter defined to yield a resinous condensation product which may vary in 'hardnessfrorn soft pliable masses to hard, brittle solids and which normally have clear, transparent properties and in somecases acolor ranging from light to darker shades of amber.

The reaction mechanism, by means of which the present resinous products are believed to be formed, presumably involves the condensation of one or both the amide groups present in the polysulfonamide or keto-amide reactants (depending upon reaction conditions and whether an unsubstituted or an -N-substituted sulfonamide is employed types of 'keto-amides utiliza'ble in the present condensation reaction), there may appear one or more monomer condensate-units in accordance with the following equation in which the products'have one or more of the structures given in Formulas A, B, C, D, E, and F shown in the equation. In addition, structural units arising from the interaction of (l) and (2) may also be present,

as taught in our aforementioned copending application. Similar structural formulae may-be shown 'as illustrative of the typesof linkages obtained in the condensation-of a polysulfonamide reactant.

a' 't hn soha +1120 where R-' is hydrogen.

a ketocarboxamide-with an aromatic polyketone and/or branched chain structure in which at least some where R is hydrogen.

(E) Ill R -N-so,R"d=Nsi-R where R is hydrogen.

where R is not hydrogen.

In the above formulas Ar is an aromatic nucleus, R, -R' and R each may represent an alkyl, cycloalkyl, aryl,

alkenyl, aralkyl, or alicyclic radical, R and R each represents one of the foregoing radicals or hydrogen, R

represents a divalent radical selected from the group cousisting of alkylene, cycloalkylene, arylene and aralkylene, a divalent heterocyclic radical, or a polyvalent radical derived from these, and n is a whole numeral from 1 to 4. The aromatic nucleus, Ar may be derived from the mono or polynuclear aromatics such as benzene, diphenyl,

.greater than two participate in the reaction and when one hydrogen atom from one of the amide groups and another hydrogen atom from a second amide group, the

amide groups being either on the same or on difierent polysulfonamide molecules or on a ketoamide molecule, condense with a single keto group of the aromatic polyketone or keto-amide reactant. When the so-called cross-linking effect is obtained, depending upon the re- .action conditions and the type of polysulfonamide and 'ketoamide charged, the resulting resinous product is a high molecular weight molecule containing a highly of the linkages are believed to be in non-linear relationship to each other and wherein the linkages are believed to extend between chains or adjacent condensate units of the keto-amide condensation product resin molecule. On the other hand when the type of linkage shown by Formula A above is obtained as a result of the condensation of a keto group with a single amido group, or when each reactant molecule has a functionality not greater than two, the resinous condensate is a linear chain-like molecule, giving rise to a thermoplastic type of resin comprising a number of condensate units joined in a continuous chainlike or linear fashion and forming a polymer of said condensate units which may be fused at a reasonably low temperature and which is relatively soluble in organic solvents. Usually, all types of the above structural arrangements or linkages shown are present in a given resinous product, although when a large number of crosslinking arrangements are present in the resinous product, the latter is likely to be thermosetting, form a product which is insoluble in organic solvents.

The reactant herein referred to as the aromatic polyketone which when reacted with a keto-amide alone or in combination with a polysulfonamide forms the present resinous condensation product, is defined structurally as a compound containing an aromatic nucleus which is either mono nuclear (that is, benzenoid) in structure or poly-nuclear, the former being represented as derived from benzene and the latter as being derived from such poly-nuclear aromatics as for example naphthalene, anthracene, phenanthrene, etc. Polyketones derived from heterocyclic aromatic compounds, as for example, quinoline, coumarone, benzothiofuran, carbazole and the like are also suitable reactants of this class. The aromatic polyketone is further characterized as being substituted on at least one of the nuclear positions of the aryl radical by an acyl group and/or a radical containing one or more keto groups, the total number of keto groups being and is likely to V at least two. The indicated aromatic polyketone may be represented by such compounds as 0-, m-, or p-diacetylbenzene, the various diacetyldiphenyls, 0-, m, or p-acetylbenzophenone, benzil or benzil-like compounds wherein the keto groups are separated by an intervening alkylene group (as, for example, in dibenzoylmethane) and others of the class containing two or more keto groups or containing other radicals such as alkyl, alkenyl, aryl, cycloalkyl, amino, halo, nitro, hydroxy, carboxy, alkoxy, acyloxy or sulfo substituents. In general, however, we prefer to employ polyketones in which the keto groups are the sole amide-reactive groups, as the condensation reaction is more readily controllable in such cases. The molecular weight and number of keto groups in the aromatic polyketone reactant determines the molecular weight of the resultant resinous condensation product. Any number of keto groups may be present in the arcmatic polyketone, and its molecular weight is limited only by practical considerations, such as its melting point, which ordinarily must be sufficiently low for the compound to melt at the reaction temperature and mix with the other reactants.

The reactant herein specified as a polysulfonamide utilized as one of the alternative reacting materials in the present condensation reaction to form the resinous product of this invention, may be selected from the aliphatic, alicyclic, heterocyclic or aromatic polysulfonamides which may further be saturated or unsaturated in character. The polysulfonamides may also be mono-substituted on one or more of the amido nitrogen atoms by alkyl, aryl, aralkyl, cycloalkyl or heterocyclic groups and may contain one or more radicals other than said sulfonamide groups attached to the hydrocarbon residue of the sulfonamide molecule such as amino, halo, alkoxy, hydroxy, carboxy, nitro or acyloxy groups as well as the thio acid and carboxylic acid amide radicals, the latter groups when present in the structure of a polysulfonamide generally altering the physical and chemical properties .of the ultimate resinous condensation product obtained in the process of this invention. It is preferred, however, that any other substituent be non-reactive with keto groups, so that the sulfonamide groups are the only ketoreactive groups present in the sulfonamide molecule. Typical representative examples of the polysulfonamide reactants utilizable in the condensation reaction of the present process, comprising, however, merely representative examples of the types specified above are such compounds as 1,2-ethanedisulfonamide, as exemplary of the aliphatic, saturated polysulfonamides, 4,5-disulfonamidohexene-Z, representing the aliphatic unsaturated polysulfonamide; ethane-1-sulfonamide-2-(N-methyl) sulfonamide, an N-substituted sulfonamide; 1,3-cyclohexane-disulfonamide and 3,5-di-sulfonamido-cyclohexene-l, representing the saturated and unsaturated alicyclic polysulfonamide; p-benzeuedi-sulfonamide, representing an aryl polysulfonamide; l sulfonamido 2-(m-sulfonamido)- phenylethane, an aralkyl polysulfonamide; 2,4-pyridinedisulfonamide of the heterocyclic polysulfonamide; and

his (2-chloro-4-sulfonamido-benzenesulfonyl) amide as a representative polysulfonamide substituted on the aryl nucleus by non-reactive radicals, and others.

Of the many types and classes of polysulfonamides utilizable as reactants in the present process, it is characteristic of said compound that the amido nitrogen also has attached thereto at least one and preferably two hydrogen atoms capable of condensation with the keto group of the aromatic polyketone reactant or the keto group of the keto amide reactant to form the resinous condensation product herein described. If mono N-substituted polysulfonamides are utilized as reactants, the substituent may be such radicals as alkyl, alkenyl, aryl, aralkyl or alicyclic groups which may be further substituted with radicals such as hydrox carboxy, nitro,

the'organic residue of the poly-sulfonamide, ketoamide gramme or aromatic polyketone reactants, such as compounds containing alkenyl and/or alkadienyl groups, generally renders the resinous condensation product subject to further polymerization, as for example, at high temperatures and in general, alters the physical properties of the product. The products from reactants containing unsaturated linkages or groups are generally of higher melting point, and are frequently more brittle or are more highly elastic than products formed from substantially saturated reactants.

The class of compounds designated herein as ketoamides and utilizable as one of the reactants condensable with another molecule of the same compound, withv another member of the same class of compounds or with an aromatic polyketone and/or a polysulfonamide to form the present resinous materials may be selected broadly from the keto-substituted sulfonamides, carboxamides and the thio acid amides andmay be of saturated or unsaturated aliphatic oraromatic structure and the aromatic may be of monoor polynuclear structure. The molecular structure of the ketoamide compounds useful as suitable reactants in the present resinifying reaction are, in general, qualified by the requirement that the keto and amide substituents are spacially separated by a sufiicient number of carbon atoms to obviate their intra-condensation within the same molecule to thereby eliminate independent ring closure between the amide and keto groups at the resin-forming reaction conditions specified for the present process. Intramolecularor self-condensation of the keto and amide groups within the same reactant molecule is to be distinguished from the type of condensationcharacterized as intermolecular condensation of the keto and amide substituents on different molecules of the ketoamide reactant derived from either the same or different ketoamide compounds charged to the reaction. Thus, in intraor self-condensation, a ring closure occurs in a single molecule of the ketoamide at. the resinifying reaction conditions, whereas in the desired inter-condensation occurring when utiliz ing compounds of the qualified structure herein provided, the keto group on one molecule of the ketoamide may condense independently of the amide group in the same molecule of ketoamide, thereby forming a bridge or bond between different molecules of the reactants. In order to obviate undesirable intraor self-condensation of the ketoamide reactant, the keto and amide substituentsmust be separated by at least three carbon atoms in the aromatic series of ketoamides, and by at. least four carbon atoms in the aliphatic and saturated alicyclic series of ketoamides. Thus, in the benzene series, the amide and keto substituents, if nuclearly substituted, must be at least meta and may be para to each other, but should not be in ortho position, unless the keto and/or amido groups are substituted on an alkyl, alkenyl or aryl side chain substituent on the aryl nucleus. Cyclization between the amido and keto groups to eliminate water of condensation occurs more readily in the aliphatic and alicyclic series and it is therefore essential that the condensable groups be substituted on more widely separated carbon atoms in the chain in order to obviate said cyclization or ring closure. Typical representative ketoamides utilizable as reactants condensable with themselves or'with anaromatic polyketone and/ or a polyamide include such compounds as mand p-acetylbenzene-sulfonamide, mand p-acetylbenzenecarboxamide, 4,4-carbamylbenzophenone, mand p-sulfonamidophenylacetone, the acetyl- (N-methyl) benzenedi-sulfonamides, 1-acetyl-4-sulfonamidocyclohexane, 1-carbamylbutylmethylketone, 2-sulfonamidohexylrnethylketone, 1 acetyl-3-thiocarbamidopropane, and others of aromatic, aliphatic, alicyclic, and heterocyclic structure.

It is a further general requisite of the polysulfonamide, the aromatic polyketone, and ketoamide reactants that they melt at temperatures below the condensation reaction temperature hereinafter specified, thereby enabling the reactant tobe initiinately mixed while in a molten state and permitting'the respective: mile and keto functtonal groups thereof to come into inter-molecular contact and efiFect condensation of the reacting components. Alternatively; the reactant may" bev dissolved in a suitable solvent which mutually dissolves the reactants and thus permits the requisite. inter-molecular contact of the amide and keto functional groups.

The condensation reaction. involved 1nthe present process is elfected at temperatures of from about 50 to about 350 C., the lower temperature limits of the above range being. provided for reactants having low melting points, such as the low molecular weight polysulfonamides and" the aromatic polyketones and for those reactants which condense rapidly at. mild temperature conditions. The reaction is undesirably sluggish below about 50 C., and temperatures above about 350 C. result in excessive decomposition and degradation re actions. In thecase. of the less reactive starting materials of those reactants having a high melting point, the-mixture of reactants is desirably heated to temperatures within theupper limits of the above temperature range to" effect condensation at areasonably rapid rate. In some instances, especially in case one of the above classes of starting materials melts at 'a high temperature, it will be preferable to employ a low-melting compound for the other class of starting material. Thus, the low-melting reactant While in a molten state dissolves the reactant or reactants melting at a high temperature and permits the intimate'ad'mixture desirable for obtaining reaction between the functional groups of the reactants. Usually it is not necessary to employ superatmospheric pressures in carrying out the reaction,except in case of utilizing a low boiling reactant and/or a high temperature to efiect the reaction when it becomes desirable to maintain v thelatter'material in liquid phase during the reaction.

In some cases it may be advantageous to employ catalyst of an acidic or dehydrating nature, such as zinc chloride, hydrogen chloride, and the like. The proportion of reactants employed in the condensation will vary in accordance with the type and number of amide groups and keto groups in each of the respective reactants. In thecase of a polysulfonamide reactant in which the amide groups are not substituted by non-condensable groups (that is, groups other than hydrogen, such as alkyl or aryl), equimolecular proportions of the aromatic polyketonewill theoretically react with a givenproportion of polysulfonamide or N substituted ketoamide reactant in which the combined number of N-substituted amide groups in the ketoamide and polysulfonamide is the same as the number of keto groups in both the aromatic polyketone and the ketoamide. In the case of a polysulfonamide and/or ketoamide reactant in which all of the amido nitrogen atoms are mono-substituted by a noncondensable group, the corresponding theoretical ratio of reactants is two sulfonamide groups to each ketone group. Expressed in another manner, it may be said that the ketone group is mono-functional with respect to a sulfonamido group (-SO:NH2) orcarbamyl .group (HzNCO-) and'bifunctional with respect toan alkyl substituted amido group (-SOzNHR, or RHNCO, where R"-is alkyl, aryl, aralkyl, alkenyl, cycloalkyl, etc.); and the proportions of reactants are so adjusted that there are at least equifunctional amounts of keto and amide groups, preferably'up to about two reactive equivalents of said keto groups to said amide groups.

It is within the scope of the present invention to effect the condensation reaction in the presence of a solvent which is miscible with the reactive starting materials and/ or the resinous product. The solvent, when utilized, may be selected from hydrocarbons having suitable boiling' points such as hexane, benzene, petroleum ether and in some cases inert non-hydrocarbon solvents such as diphenyloxide, other ethers such'as dipropyl ether, dibutyl ether, etc; It is preferred to utilize a solvent which boils at a temperature above the reaction temperature required for the condensation reaction, although in some instances, the solvent may be present in the reaction mixture for the express purpose of providing a refluxing medium which maintains the temperature of reaction at a constant value, the boiling point of the solvent. The solvent may also be expressly added to the reaction mixture to form an azeotrope with the water liberated during the condensation reaction, thus providing a means for removing the latter by-product from the reaction mixture, either during the condensation reaction or following the formation of the product. In many cases, it is desirable to employ the solvent as a diluent of the reactants so as to control the rate of reaction or the temperature developed in the reaction mixture. When such precautions are taken, the product usually has a more desirable color and its other physical properties, such as flexibility and hardness are improved.

After completion of the initial condensation reaction and the separation of the product thereof from the reaction mixture, the resin may be dried and pulverized into a finely divided condition suitable for subsequent molding operations, mixing into protective or covering compositions or for utilization in the manufacture of other compositions, such as plastics. In case an excess of either reactant is employed in the condensation reaction, or if the initial stage of the reaction is not allowed to proceed to complete condensation of the components, the reaction product separated from the initial stage of the condensation may be further reacted with additional quantities of one or more of the reactants to form thereby a product having properties differing from the initial or partial condensation product. Alternatively, the excess of reactant may be removed from the product by extraction with a suitable solvent, for example, one which is miscible with either the excess reactant or with the resinous product to effect thereby a separation of these components from the partial condensation product. The final stage of the reaction or completion of the condensation of the reactants present in the partially condensed product may be conducted in a heated mold or other shaping apparatus when desired. A convenient means for forming molded articles is to conduct the initial reaction to a stage of partial completion, forming thereby a soft, resinous product which usually possesses thermoplastic properties and thereafter completing the reaction by heating the initial reaction product in the desired mold, thus forming the thermosetting resinous product of this invention which is relatively little deformed at a high temperature and in general is tougher than the initial or partial condensation product.

Resinous products obtained in the present process have widespread utility in various alts, depending in large measure upon the physical properties of the product. The resins, for example, may be composited with various drying oils such as the glyceride type or unsaturated hydrocarbon type to form varnish and/ or paint compositions, and when employed for said purposes, the resins contribute valuable film-forming and bodying properties to such compositions. The protective coatings prepared from the present resins form a glossy surface resistant to chemicals, water and abrasive agents and such coating compositions in which the solid resins of this invention are incorporated dry to hard non-tacky films. In some cases, the products of this invention are useful as plasticizers, especially when the product is a semi-solid or viscous liquid resin. When solid resinous products of the thermoplastic type are obtained, these may be melted or extruded into variously shaped articles or used to impregnnte cellulosic materials such as paper or shaped wooden articles, or the resin may be heated with wood flour, wood chips, cotton linters, asbestos or other fibrous materials to form semi-rigid or rigid structural shapes.

The following examples are introduced for the purpose of illustrating the present process and the properties of 8 the products obtained from the condensation of typical reactants as disclosed herein. In thus citing specific applications of the invention, it is not intended thereby to limit the generally broad scope of the invention in accord ance with the'conditions and reactions utilized therein.

Example 1 A mixture of 16.2 g. of p-diacetylbenzene, 23.6 g. of m-benzenedisulfonamide and 18.5 g. of p-acetylbenzenesulfonamide was heated in a nitrogen atmosphere at l45-l50 C. for 3.5 hours. The resultant yellowish solid, on cooling, was a tough resin of softening point about 250-265 F.

A similar mixture was refluxed in commercial xylene cc.) until the solution became cloudy, and the vapors were then slowly distilled overhead until the water layer of the condensed vapors reached a volume of about 5.1 cc. The xylene was thereupon removed in vacuo, leaving a product which was lighter in color than that formed above and which did not soften in boiling water or at higher temperatures, up to about 150 C.

Example H A mixture of 52.4 grams (0.2 moles) of 1-acetyl-2,4- benzenedisulfonamide and 16 grams (0.1 mole) of mdiacetylbenzene was dissolved in 250 cc. of xylene and the mixture refluxed at the boiling point of xylene for six hours an overhead distillate comprising water vapor being taken from the top of the reflux condenser as the reflux distillation continued. The condenser was then removed, the xylene solvent distilled off and the residue heated under vacuum to remove the remaining xylene vapor. The residual resinous product is a light tan-colored, thermosetting resin having a softening point above the boiling point of water.

Example 111 A mixture of p-benzenedicarboxamide (16.5 gr. or 0.1 mole) and p-diacetylbenzene (16 grams or 0.1 mole) was heated in a refluxing solution thereof in xylene for six hours and the resinous product recovered in accordance with the procedure described above. The residue left after evaporation of the xylene solvent consisted of a substantially clear, colorless solid having a softening point above the boiling point of water.

We claim as our invention:

1. A process for the preparation of a resinous material which comprises reacting at a condensation temperature of from about 50 to about 350 C. a non-intracondensable ketoamide selected from the group consisting of the-keto-substituted sulfonarnides, carboxamides and thio acid amides with an aromatic polyketone in which the keto groups are the only reactive groups and a polysulfonamide in which sulfonamide groups are the only reactive groups and in which each sulfonarnide group contains at least one hydrogen atom attached to the nitrogen atom of the group.

2. A process for the preparation of a resinous material which comprises reacting at a condensation temperature of from about 50 to about 350 C. a non-intracondensable aromatic ketoamide in which the keto and amido substituents-are present on nuclear aryl groups separated by at least one nuclear carbon atom with at least one compound selected from the group consisting of an arcmatic polyketone in which the lteto groups are the only reactive groups and a polysulfonamide in which the sulfonamide groups are the only reactive groups and in which each sulfonaruide group contains at least one hydrogen atom attached tothe nitrogen atom of the group.

3. The process of claim 1 further characterized in that said aromatic polyketone is a diacetylbenzene.

4. The process of claim 2 further characterized in that said compound is a diacetylbenzene.

5. The process of claim 1 further characterized in that said polysulfonamide is a benzene disulfonamide.

6 The process of claim 2 further characterized in that said compound is a benzene disulfonamide.

7. The process of claim 1 further characterized in that said reaction is executed in the presence of an inert organic solvent in which said ketoamide, aromatic polyketone and polysulfonamide are soluble in the proportions utilized in the process.

8. The process of claim said solvent is xylene.

9. The resinous condensation product resulting from the reaction at a condensation temperature of from about 50 to about 350 C. of a non-intracondensable ketoamide selected from the group consisting of the ketosubstituted sulfonamides, carboxamides and thio acid amides with an aromatic polyketone in which the keto groups are the only reactive groups and a polysulfonamide in which the sulfonamide groups are the only reactive groups and in which each sulfonamide group contains at least one hydrogen atom attached to the nitrogen atom of the group.

10. The resinous condensation product resulting from the reaction at a condensation temperature of from about 50 to about 350 C. of a non-intracondensable aromatic ketoamide in which the keto and amido substituents are present on nuclear aryl groups separated by at least one nuclear carbon atom with at least one compound 7 further characterized in that ketone in which the keto groups are the only reactive groups and a polysulfonamide in which the sulfonamide groups are the only reactive groups and in which each sulfonamide group contains at least one hydrogen atom attached to the nitrogen atom of the group.

11. The resinous condensation product resulting from the reaction at a condensation temperature of from about to about 350 C. of a non-intracondensable aromatic ketoamide in which the keto and amido substituents are present on nuclear aryl groups separated by at least one nuclear carbon atom with an aromatic polyketone in which the keto groups are the only reactive groups and a polysulfonamide in which the sulfonamide groups are the only reactive groups and in which each sulfonamide group contains at least one hydrogen atom attached to the nitrogen atom of the group.

References Cited in the file of this patent UNITED STATES PATENTS 

2. A PROCESS FOR THE PREPARATING OF A RESINOUS MATERIAL WHICH COMPRISES REACTING AT A CONDENSATION TEMPERATURE OF FROM ABOUT 50* TO ABOUT 350* C. A NON-INTRACONDENSABLE AROMATIC KETOAMIDE IN WHICH THE KETO AND AMIDO SUBSTITUENTS ARE PRESENT ON NUCLEAR ARYL GROUPS SEPARATED BY AT LEAST ONE NUCLEAR CARBON ATOM WITH AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN AROMATIC POLYKETONE IN WHICH THE KETO GROUPS ARE THE ONLY REACTIVE GROUPS AND A POLYSULFONAMIDE IN WHICH THE SULFONAMIDE GROUPS ARE THE ONLY REACTIVE GROUPS AND IN WHICH EACH SULFONAMIDE GROUP CONTAINS AT LEAST ONE HYDROGEN ATOM ATTACHED TO THE NITROGEN ATOM OF THE GROUP. 